Silica supports with high aluminoxane loading capability

ABSTRACT

Olefin polymerization catalyst systems having high aluminoxane loading and methods for making and using them are disclosed herein.

CROSS REFERENCE TO RELATED APPLICATIONS

This invention claims priority to and the benefit of U.S. Ser. No.62/205,977, filed Aug. 17, 2015 and U.S. Ser. No. 62/171,602, filed Jun.5, 2015.

FIELD OF THE INVENTION

This invention relates to olefin polymerization catalyst systemscomprising silica supports with high aluminoxane loading capability,methods for producing such catalysts systems, and methods forpolymerizing olefins using such catalyst systems.

BACKGROUND OF THE INVENTION

The discovery of metallocene catalysts activated with aluminoxanes hasenabled the synthesis of new polyolefins with improved properties. Asignificant disadvantage of metallocene catalysts, however, is therequirement of large amounts of often expensive co-catalyst (such as analuminoxane) to activate the catalysts. Additionally, while homogeneousmetallocene catalysts can be used in solution phase reactors, themetallocene catalyst compounds generally need to be supported to be usedin most other polymerization processes. Thus, while many metallocenecatalysts are capable of making polyolefins with commercially desirableproperties, the catalysts are often not practical or economical on anindustrial scale due to the large amount of co-catalyst needed anddifficulties in incorporating the catalyst and co-catalyst on a support.

It is important to find a way to incorporate the metallocene andco-catalyst onto the support without losing the advantages of thehomogenous metallocene compound, including high catalyst activity,stereochemical control, and the ability to tailor polymer properties.Identifying the optimum properties for metallocene catalyst supports isan area of significant research interest. Both the nature of the supportand the method used to integrate the support and/or co-catalyst canaffect the catalyst activity and the final properties of the polymer.

Although aluminoxanes are expensive, silica supported catalysts withhigher aluminoxane loadings are desirable in some circumstances. Forexample, when the metallocene compound has low activity or lowactivation efficiency or when a multi-catalyst precursor system is usedwhere the total catalyst precursor loadings are higher than usual,higher aluminoxane loading may be required to achieve a commerciallyviable catalyst activity. In polymerization processes where liquidsolvent is present, such as slurry and condensed mode processes, MAO issoluble in the solvent and can leach out of the silica particles. It isnot possible with conventional silicas, e.g., Grace 948 or 955, PQ ES 70or ES 757, to load more than about 8 to 9 mmol Al/g of silica onto thesupport without leaching of MAO (and possibly catalyst) into the solventmedium. This leaching can cause fouling and fines in the reactor systemand can negatively impact catalyst activity and polymer properties.

It is also important for a catalyst support to be able to retainmechanical strength under the operating conditions of the process inwhich it is used. Many polymerization processes take place atsignificantly higher than ambient temperatures and pressures. If themechanical strength of the support is compromised, the impregnatedsilica particles can fragment. This can also lead to activator andcatalyst leaching into the solvent medium. Additionally, polymerizationcan start to take place on the smaller fragmented particles, leading toagglomerates within the reactor system that can cause fouling, plugging,and other problems.

Pullukat, T. J., et al., “Microspherical Silica Supports with High PoreVolume for Metallocene Catalysts,” presented at Metallocenes Europe '97,Dusseldorf, Germany, Apr. 8-9, 1997, pp. 1-11 discloses silica gel beadswith a pore volume of 3.0 cc/g. It is said that the higher pore volumesof these silicas allow for greater versatility in preparing high surfacearea supports. Metallocene catalysts using these high pore volumesilicas are disclosed with an MAO loading of 7 mmol Al/g silica.

U.S. Pat. No. 6,001,764 discloses a non-metallocene Ziegler-Natta basedcatalyst component on a silica support having high pore volume and highsurface area. The catalytic component comprises a complex product of atransition metal halide and a metal alkyl which excludescyclopentadienyl. The examples do not use an aluminoxane co-catalyst,and no mention is made of aluminoxane loading.

Thus, there is a need for catalyst systems, particularly metallocenecatalyst systems, with supports having higher aluminoxane loadingcapabilities that are capable of maintaining the mechanical strengthnecessary for a variety of polymerization processes.

SUMMARY OF THE INVENTION

The invention is directed to olefin polymerization catalyst systemscomprising a porous silica support, wherein the porous silica supportcomprises silica gel particles having an average surface area of fromabout 400 to 800 m²/g, an average pore diameter of from about 60 to 200Angstrom, and at least 20% of the incremental pore volume comprised ofpores having a pore diameter larger than about 100 Angstrom. Thecatalyst system further comprises an aluminoxane, and the aluminoxaneloading on the support is greater than about 9.5 mmol Al/g silica.

The invention is also directed to methods for producing an olefinpolymerization catalyst system, the methods comprising contacting: i) aporous silica support, wherein the porous silica support comprisessilica gel particles having an average surface area of from about 400 to800 m²/g, an average pore diameter of from about 60 to 200 Angstrom, andat least 20% of the incremental pore volume comprised of pores having apore diameter larger than about 100 Angstrom; ii) an aluminoxane; andiii) an olefin catalyst component, wherein the aluminoxane loading onthe support is greater than about 9.5 mmol Al/g silica.

The invention is also directed to methods for polymerization of olefinsusing the catalyst systems disclosed herein. The catalyst system maycomprise a single site catalyst system. The catalyst system may alsocomprise a metallocene catalyst system.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an electron micrograph of raw PD 14024 silica.

FIG. 2 is an electron micrograph of MAO supported on PD 14024 silica,with an aluminoxane loading of 13.2 mmol Al/g silica.

FIG. 3 is a plot of the pore diameter distribution for raw PD 14024silica versus MAO supported PD 14024 silica at different MAO loadings.

FIG. 4 is an electron micrograph of raw Fuji P-3 silica.

FIG. 5 is an electron micrograph of MAO supported on Fuji-P-3 silica,with an aluminoxane loading of 12.5 mmol Al/g silica.

FIG. 6 is a plot of the pore diameter distribution for raw AGC D150-60Asilica.

FIG. 7 is an electron micrograph of MAO supported on AGC D150-60A silicaprepared at high temperature, after heat treatment, and where MAO solidleaching has occurred.

FIG. 8 is an electron micrograph of MAO supported on AGC D150-60A silicaprepared at low temperature.

FIG. 9 is an electron micrograph of raw PQ MS 3065 silica after ascratch with a lab spatula.

FIG. 10 is an electron micrograph of MAO supported on PD 13054 silica,with an aluminoxane loading of 11.4 mmol Al/g silica and where MAO solidleaching has occurred.

DEFINITIONS

For purposes of this disclosure and the claims appended thereto, the newnumbering scheme for the Periodic Table Groups is used as described inCHEMICAL AND ENGINEERING NEWS, 63(5), p. 27, (1985).

For purposes herein, particle size (PS) or diameter, and distributionsthereof, are determined by laser diffraction using a MASTERSIZER 3000(range of 1 to 3500 μm) available from Malvern Instruments, Ltd.,Worcestershire, England, or an LS 13 320 MW with a micro liquid module(range of 0.4 to 2000 μm) available from Beckman Coulter, Inc., Brea,Calif. Average PS refers to the distribution of particle volume withrespect to particle size. Unless otherwise indicated expressly or bycontext, “particle” refers to the overall particle body or assembly suchas an aggregate, agglomerate, or encapsulated agglomerate, rather thansubunits or parts of the body, such as the primary particles inagglomerates or the elementary particles in an aggregate.

For purposes herein, the surface area (SA, also called the specificsurface area or BET surface area), pore volume (PV), and pore diameter(PD) of catalyst support materials are determined by theBrunauer-Emmett-Teller (BET) method using adsorption-desorption ofnitrogen (temperature of liquid nitrogen: 77 K) with a MICROMERITICSTRISTAR II 3020 instrument or MICROMERITICS ASAP 2420 instrument afterdegassing of the powders for 4 to 8 hours at 100 to 300° C. forraw/calcined silica or 4 hours to overnight at 40 to 100° C. for silicasupported aluminoxane. More information regarding the method can befound, for example, in “Characterization of Porous Solids and Powders:Surface Area, Pore Size and Density,” S. Lowell et al., Springer, 2004.PV refers to the total PV, including both internal and external PV.

The following abbreviations may be used herein: Me is methyl, Et isethyl, Pr is propyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl,sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, Bn isbenzyl, MAO is methylaluminoxane, MCN is metallocene, RT is roomtemperature (e.g., about 20-25° C.).

A “catalyst system” is a combination of at least one catalyst precursorcompound, at least one activator, an optional co-activator, and asupport material. A polymerization catalyst system is a catalyst systemthat can polymerize monomers to polymer.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise, the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a radical, which contains hydrogen atoms and up to 100carbon atoms and which may be linear, branched, or cyclic, and whencyclic, aromatic or non-aromatic.

A substituted hydrocarbyl radical is a hydrocarbyl radical where atleast one hydrogen has been replaced by a heteroatom orheteroatom-containing group.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g., F,Cl, Br, I) or halogen-containing group (e.g., CF₃).

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like, where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR*₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the like,where R* is independently a hydrocarbyl or halocarbyl radical and two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

An aryl group is defined to be a single or multiple fused ring groupwhere at least one ring is aromatic. Examples of aryl and substitutedaryl groups include phenyl, naphthyl, anthracenyl, methylphenyl,isopropylphenyl, tert-butylphenyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, carbazolyl, indolyl, pyrrolyl, and cyclopenta[b]thiopheneyl.Preferred aryl groups include phenyl, benzyl, carbazolyl, naphthyl, andthe like.

In using the terms “substituted cyclopentadienyl,” or “substitutedindenyl,” or “substituted aryl,” the substitution to the aforementionedis on a bondable ring position, and each occurrence is selected fromhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polargroup. A “bondable ring position” is a ring position that is capable ofbearing a substituent or bridging substituent. For example,cyclopenta[b]thienyl has five bondable ring positions (at the carbonatoms) and one non-bondable ring position (the sulfur atom);cyclopenta[b]pyrrolyl has six bondable ring positions (at the carbonatoms and at the nitrogen atom). Thus, in relation to aryl groups, theterm “substituted” indicates that a hydrogen group has been replacedwith a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polargroup. For example, “methyl phenyl” is a phenyl group having had ahydrogen replaced by a methyl group.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides silica supported single site ormetallocene catalyst-based olefin polymerization catalyst systemscapable of high aluminoxane loadings, and methods for making and usingsuch catalyst systems. It has been determined that a particularcombination of surface area, pore diameter, and pore diameterdistribution, among other factors, is optimum for increasing aluminoxaneloading and maintaining mechanical strength in silica supports withsingle site and metallocene catalysts.

MAO, in commercially available embodiments, often has a molecule size ofabout 15-20 Angstroms. The pore diameters must be large enough to enablethe aluminoxane to enter the pores for high MAO loadings. Smaller porediameters can cause fragmentation of the supported MAO, especiallyduring heat treatment. Also, if the pore diameters are too small, e.g.,approaching 20 Angstroms or smaller, MAO molecules will not be able toenter the pores. Pore diameters that are too large, however, can resultin highly hollow silica particles with very thin walls that do not havethe mechanical strength to maintain their structure in a catalystpreparation or polymerization environment where factors such as hightemperature, pressure, or agitation power are involved.

Additionally, the pore diameters in silica are not uniform, but ratherare a distribution of different sizes. In a common process for preparinga silica-supported catalyst system, the silica is first contacted withan aluminoxane. The silica acts like a sponge, adsorbing the aluminoxanesuch that it coats the surfaces of the silica particles and pores. Inpreparation processes, the silica is often subject to a heat treatmentafter contact with the aluminoxane, which causes the aluminoxane toexpand. The supported aluminoxane is then contacted with one or morecatalyst precursors, which react with the supported aluminoxane tobecome an active catalyst. The active catalyst is contacted with one ormore monomers in a polymerization system to form polymers. The porediameters should be of sufficient size to allow aluminoxane to enter,coat the pores, and expand during heat treatment, while leaving enoughspace for catalyst precursors and monomers to react with the supportedaluminoxane without significant mass transfer limitations. It has beendetermined that a certain pore diameter distribution, in combinationwith the other properties disclosed herein, is conducive to enablingthis. In embodiments of the invention, at least 20%, 25%, 30%, 35%, 40%,45%, 50%, 60%, 70%, 80%, 85%, or even more of the incremental porevolume, may be comprised of pores having a pore diameter larger thanabout 100, 125, or 150 Angstrom, and, optionally, smaller than about1000, 900, 800 Angstrom, including any combination of numbers disclosedherein. Additionally, in embodiments of the invention, less than 20%,15%, 10%, 5%, 2.5% or less of the incremental pore volume is comprisedof pores having a pore diameter in the range of about 1000 Angstrom ormore, about 900 Angstrom or more, or about 800 Angstrom or more.

The porous silica support may comprise silica gel particles having anaverage surface area of from about 400 to 800 m²/g and an average porediameter of from about 60 to 200 Angstrom. The average surface area mayrange from a low of about 400, 500, 530, 540, 550, or 600 m²/g to a highof about 600, 650, 700, 750, or 800 m²/g, including any combination ofany upper or lower value disclosed herein. The average pore diameter mayrange from a low of about 60, 70, 80, 90, 100, or 110 Angstrom to a highof about 120, 130, 150, 180, or 200 Angstrom, including any combinationof any upper or lower value disclosed herein.

The porous support may comprise silica gel particles having an averagepore volume of from about 0.5 to 2.5 ml/g of silica. The average porevolume may range from a low of about 0.5, 0.7, 1.0, 1.1, 1.3, or 1.4ml/g of silica to a high of about 1.5, 1.6, 1.8, 2.0, or 2.5, includingany combination of any upper or lower value disclosed herein. Theaverage pore volume may be about 0.5 ml/g, about 1.0 ml/g, about 1.5ml/g, or about any value disclosed herein. In embodiments of theinvention, a higher pore volume requires a lower surface area, orvice-versa.

The porous support may comprise silica gel particles having an averageparticle size of from about 20 to 200 micrometers. The average particlesize may range from a low of about 20, 30, 50, 70, or 80 to a high ofabout 80, 90, 100, 110, 130, or 200 micrometers, including anycombination of any upper or lower value disclosed herein.

The porous support may comprise agglomerates of a plurality of primaryparticles, the support or agglomerates preferably having an averageparticle size of at least 50 μm, or surface area less than 1000 m²/g, ora combination thereof. The agglomerates may be at least partiallyencapsulated. In an embodiment of the invention, the porous support doesnot comprise agglomerates.

The term “agglomerate” as used herein refers to a material comprising anassembly, of primary particles held together by adhesion, i.e.,characterized by weak physical interactions such that the particles caneasily be separated by mechanical forces, e.g., particles joinedtogether mainly at corners or edges. The term “primary particles” refersto the smallest, individual disagglomerable units of particles in anagglomerate (without fracturing), and may in turn be an encapsulatedagglomerate, an aggregate or a monolithic particle. Agglomerates aretypically characterized by having an SA not appreciably different fromthat of the primary particles of which it is composed. Silicaagglomerates are prepared commercially, for example, by a spray dryingprocess.

“Aggregates” are an assembly of elementary particles sharing a commoncrystalline structure, e.g., by a sintering or other physico-chemicalprocess such as when the particles grow together. Aggregates aregenerally mechanically unbreakable, and the specific surface area of theaggregate is substantially less than that of the correspondingelementary particles. An “elementary particle” refers to the individualparticles or grains in or from which an aggregate has been assembled.For example, the primary particles in an agglomerate may be elementaryparticles or aggregates of elementary particles. For more information onagglomerates and aggregates, see Walter, D., PrimaryParticles—Agglomerates—Aggregates, in Nanomaterials (ed DeutscheForschungsgemeinschaft), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim,Germany, doi: 10.1002/9783527673919, pp. 1-24 (2013).

The terms “monolith” or “monolithic” refer to a material formed of asingle mass of material, and include aggregates, as well as bulkmaterials, without any defined geometry or grain structure. FIG. 3 showsa comparative support MS 3050, comprised of generally sphericalparticles 20 with an entirely aggregated or monolithic core 22, lackingthe agglomerated primary particles and internal pore morphology of theFIG. 1-2 supports.

The terms “capsule” or “encapsulated” or “microencapsulated” are usedinterchangeably herein to refer to an agglomerate in the 1-1000 μm sizerange comprising an exterior surface that is coated or otherwise has aphysical barrier that inhibits disagglomeration of the primary particlesfrom the interior of microencapsulated agglomerate. The barrier orcoating may be an aggregate, for example, of primary and/or elementaryparticles otherwise constituted of the same material as the agglomerate.FIGS. 1-2 show examples of microencapsulated agglomerates 10 comprisedof a plurality of primary particles 12 within an outer aggregate surfaceor shell 14 that partially or wholly encapsulates the agglomerates, inwhich the primary particles may be allowed to disagglomerate byfracturing, breaking, dissolving, chemically degrading or otherwiseremoving all or a portion of the shell 14.

In the case of spray dried, amorphous, hydrated-surface silica as oneexample, the agglomerates 10 may typically have an overall size range of1-300 μm (e.g., 30-200 μm), the primary particles 12 a size range of0.001-50 μm (e.g., 50-400 nm or 1-50 μm), and the elementary particles asize range of 1-400 nm (e.g., 5-40 nm). As used herein, “spray dried”refers to metal oxide such as silica obtained by expanding a sol in sucha manner as to evaporate the liquid from the sol, e.g., by passing thesilica sol through a jet or nozzle with a hot gas.

The porous support may comprise silica gel particles having anycombination of properties disclosed herein. For example, the poroussupport may comprise silica gel particles having an average surface areaof about 600 m²/g and an average pore diameter of about 90 Angstrom, oran average surface area of about 550 m²/g and an average pore diameterof about 110 Angstrom.

The combination of properties disclosed herein enables silica supportswith high aluminoxane loadings. For example, the aluminoxane loading onthe porous silica support may be greater than about 9.5, 10, 12, 14, or18 mmol Al/silica. The aluminoxane loading may range from a low of about9.5, 10, 11, 12, 13, 14, 15, or 16 mmol Al/g silica to a high of about12, 14, 16, 18, or 20 mmol Al/g silica, including any combination of anyupper or lower value disclosed herein.

For purposes herein, the term “aluminoxane loading” is the amount ofaluminoxane in the silica supported aluminoxane that is adhered tosilica particles. The aluminoxane may be adhered within the outer orinner pores of the particles, adhered to the surface of the particles,or otherwise adhered to the particles. Aluminoxane loading may berepresented as mmol Al/g silica.

Certain processes for preparing a silica supported aluminoxane, such asthe high temperature process designated as sMAO Method A in theExperimental section (or similar high temperature processes), can causeparticle fragmentation and/or aluminoxane leaching with certain silicas.This is more likely to occur in silicas with smaller average porediameters, such as with silicas having average pore diameters rangingfrom about 60 to about 80 Angstrom. In embodiments of the invention,these fragmented silica supported aluminoxanes have very highaluminoxane loadings. Without wishing to be bound by theory, it isbelieved that there are two possible mechanisms contributing to thesehigh aluminoxane loadings. First, the particle fragmentation caused byheating may open up additional silica pores for aluminoxane entry andthus lead to higher aluminoxane loadings. Second, the larger amount ofsmall pores, similar in size to the MAO molecules, present in silicashaving smaller average pore diameters limits the expansion of solid MAOinto the pores. This limitation may force aluminoxane out of the pores,leading to the formation of new aluminoxane-rich solid particles. Insum, whatever the mechanism is, the increased aluminoxane loading inthese fragmented silica supported aluminoxanes may contribute to veryhigh catalyst activities in certain applications.

Although these fragmented silica supported aluminoxanes may not besuitable for some catalyst preparation or polymerization systems, theymay be suitable and even potentially quite valuable for others due totheir ability to contribute to high catalyst activities. For example,they may be suitable in catalyst preparation environments where highagitation power is not involved or in polymerization reactor systemswhere catalyst particle size does not play a significant role or wherealuminoxane leaching is not as likely to be problematic (e.g., gas phasepolymerization reactor systems).

Where particle fragmentation and/or aluminoxane leaching are problematicwith a given silica and it is desired to control these aspects, adifferent process for preparing the silica supported aluminoxane may beused. For example, the process designated as sMAO Method B in theExperimental section or a similar process where the reaction temperaturefor contacting the silica and aluminoxane is controlled at a lowertemperature may be used. This may reduce the fragmentation and leaching,but may also reduce the aluminoxane loading.

Thus, in embodiments of the invention, when the reaction temperature forcontacting the silica and aluminoxane is below about 40° C., the silicasupported aluminoxane has a first aluminoxane loading, and when thereaction temperature is above about 40° C., the silica supportedaluminoxane has a second aluminoxane loading. The second aluminoxaneloading may be greater than the first aluminoxane loading by at leastabout 1.0, 2.0, 3.0, 4.0, 5.0, or 6.0 mmol Al/g silica. For example, thesecond aluminoxane loading may be greater than the first aluminoxaneloading by in a range of from a low of about 1.0, 1.5, 2.0, 3.0, 4.0, or5.0 mmol Al/g silica to a high of about 2.0, 3.0, 4.0, 5.0, or 6.0 mmolAl/g silica, including any combination of any upper or lower valuedisclosed herein.

The aluminoxane loading on the porous silica support may also berepresented or evaluated by measuring the difference between the averagesurface area of the particles in the raw silica (referred to herein as“raw silica surface area”) and the average surface area of the particlesafter aluminoxane has been incorporated (referred to herein as“supported aluminoxane surface area”). It is preferred that these twosurface areas be similar. Hence, in embodiments of the invention, thedifference between the raw silica surface area and the supportedaluminoxane surface area may be about or less than 50%, 40%, 30%, 20%,or 10% on a volumetric basis. Both surface areas may be measured usingthe BET method described above.

The aluminoxane loading on the porous silica support may also berepresented or evaluated by the difference in average particle sizebetween the raw silica (referred to herein as “raw silica particlesize”) and the average particle size of the supported aluminoxane(referred to herein as “supported aluminoxane particle size”). It ispreferred that these two particle sizes be similar. Hence, inembodiments of the invention, the difference between the raw silicaparticle size and the supported aluminoxane particle size may be aboutor less than 50%, 40%, 30%, 20%, or 10% on a volumetric basis. Bothparticle sizes may be measured by the laser refraction method describedabove.

Preferred embodiments of the catalyst system, support, activator,catalyst precursor compound, and co-activator are described in moredetail below.

Support Materials:

The catalyst systems comprise porous solid particles as a supportmaterial to which the catalyst precursor compound and/or activator maybe anchored, bound, adsorbed or the like. The support material comprisesan inorganic oxide in a finely divided form. Suitable inorganic oxidematerials for use in MCN catalyst systems herein include Groups 2, 4,13, and 14 metal oxides, such as silica, alumina, magnesia, titania,zirconia, and the like, and mixtures thereof. Also, combinations ofthese support materials may be used, for example, silica-chromium,silica-alumina, silica-titania, and the like.

The support material comprises silica, e.g., amorphous silica, which mayinclude a hydrated surface presenting hydroxyl or other groups which canbe deprotonated to form reactive sites to anchor activators and/orcatalyst precursors. Other porous support materials may, optionally, bepresent with the silica as a co-support, for example, talc, otherinorganic oxides, zeolites, clays, organoclays, or any other organic orinorganic support material and the like, or mixtures thereof. Silicaswhich may be suitable are commercially available under the tradedesignations PD 14024, D70-120A, and the like.

When a silica support is referred to herein, the silica support in rawform comprises at least 60 wt %, 70 wt %, 80 wt %, 90 wt %, 95 wt %, 98wt %, or 99 wt % or more of silica. The silica support may comprise upto 5 wt %, 10 wt %, 20 wt %, 30 wt %, or 40 wt % of another compound.The other compound may be any other support material discussed herein.The other compound may be a titanium, aluminum, boron, magnesium, ormixtures thereof. Additionally, the other compound may be a talc, otherinorganic oxide, zeolite, clay, organoclay, or mixtures thereof. Thesilica support may also not include any substantial amount of any othercompound, i.e., the silica support comprises less than 5 wt %, 1 wt %,0.5 wt %, 0.2 wt %, or less of any other compound.

According to some embodiments of the invention, the support material isthen contacted with the activator (described in more detail below), atleast one single site catalyst precursor compound (described in moredetail below), and/or co-catalyst (described in more detail below), andoptionally, a scavenger or co-activator (described in more detailbelow).

Drying of the support material can be effected according to someembodiments of the invention by heating or calcining above about 100°C., e.g., from about 100° C. to about 1000° C., preferably at leastabout 200° C. The silica support may be heated to at least 130° C.,about 130° C. to about 850° C., or about 200° C. to about 600° C. for atime of 1 minute to about 100 hours, e.g., from about 12 hours to about72 hours, or from about 24 hours to about 60 hours. The calcined supportmaterial may comprise at least some groups reactive with anorganometallic compound, e.g., reactive hydroxyl (OH) groups to producethe supported catalyst systems of this invention.

Supportation:

The support may be treated with an organometallic compound to react withdeprotonated reactive sites on the support surface. In general, thesupport is treated first with an organometallic activator such as MAO,and then the supported activator is treated with the metallocenecompound, optional metal alkyl co-activator, although the metallocenecompound and or co-activator can be loaded first, followed by contactwith the other catalyst system components.

The support material, having reactive surface groups especially aftercalcining, may be slurried in a non-polar solvent and contacted with theorganometallic compound (activator in this example), preferablydissolved in the solvent, preferably for a period of time in the rangeof from about 0.5 hour to about 24 hours, from about 2 hours to about 16hours, or from about 4 hours to about 8 hours. Suitable non-polarsolvents are materials in which, other than the support material and itsadducts, all of the reactants used herein, i.e., the activator, and themetallocene compound, are at least partially soluble and which areliquid at reaction temperatures. Preferred non-polar solvents arealkanes, such as isopentane, hexane, n-heptane, octane, nonane, anddecane, although a variety of other materials including cycloalkanes,such as cyclohexane, aromatics, such as benzene, toluene, andethylbenzene, may also be employed.

The mixture of the support material and activator (or otherorganometallic compound) in various embodiments of the invention maygenerally be heated or maintained at a temperature of from about −60° C.up to about 130 or 140° C., such as, for example: about 40° C. or below,about RT or below, about −20° C. or below; from about 10° C. or 20° C.up to about 60° C. or about 40° C.; RT or about 25° C. or above; or fromabout 40° C., about 60° C., or about 80° C. up to about 100° C., orabout 120° C. Where the support may be susceptible to fragmentationduring activator/catalyst precursor supportation (e.g., SA≥650 m²/g,PD≤7 nm), fragmentation may be controlled through the manipulation ofreaction conditions to inhibit fragmentation, such as, at a lowerreaction temperature, e.g., −60° C.-40° C., preferably −20° C.-30° C.,to achieve <10 vol % fragmented particles, preferably <5 vol %fragmented particles; or to promote fragmentation such as at a higherreaction temperature, e.g., ≥40° C., preferably ≥60° C., to achieve >10vol % fragmented particles, e.g., 10-80 vol % fragmented particles, suchas 10-20 vol % fragmented particles, 20-70 vol % fragmented particles,70-90 vol % fragmented particles, >90 vol % fragmented particles, or thelike. In general, the time and temperature required to promotefragmentation are inversely related, i.e., at a higher temperature,debris dominated fragmentation may require a shorter period of time.

The supported activator may, optionally, be treated with anotherorganometallic compound, which is also selected as the scavenger,preferably a metal alkyl such as an aluminum alkyl, to scavenge anyhydroxyl or other reactive species that may be exposed by or otherwiseremaining after treatment with the first organometallic compound, e.g.,hydroxyl groups on surfaces exposed by fragmentation may be reacted andthereby removed by contact of the fragments with an aluminum alkyl suchas triisobutylaluminum (TIBA). Useful metal alkyls which may be usedaccording to some embodiments of the invention to treat the supportmaterial have the general formula R_(n)-M, wherein R is C₁-C₄₀hydrocarbyl such as C₁-C₁₂ alkyl, for example, M is a metal, and n isequal to the valence of M, and may include oxophilic species such asdiethyl zinc and aluminum alkyls, such as, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum and the like, includingcombinations thereof. Then the activator/support material is contactedwith a solution of the catalyst precursor compound. In some embodimentsof the invention, the supported activator is generated in situ. Inalternate embodiments of the invention, the slurry of the supportmaterial is first contacted with the catalyst precursor compound for aperiod of time in the range of from about 0.5 hour to about 24 hours,from about 2 hours to about 16 hours, or from about 4 hours to about 8hours, and the slurry of the supported MCN compound is then contactedwith an organometallic-activator solution and/ororganometallic-scavenger solution.

Activators:

Activators are compounds used to activate any one of the catalystprecursor compounds described above by converting the neutral catalystprecursor compound to a catalytically active catalyst compound cation.Preferred activators include aluminoxane compounds, including modifiedaluminoxane compounds.

Aluminoxanes are generally oligomeric, partially hydrolyzed aluminumalkyl compounds containing —Al(R1)-O— subunits, where R1 is an alkylgroup, and may be produced by the hydrolysis of the respectivetrialkylaluminum compound. Examples of aluminoxane activators includemethylaluminoxane (MAO), ethylaluminoxane, butylaluminoxane,isobutylaluminoxane, modified MAO (MMAO), halogenated MAO where the MAOmay be halogenated before or after MAO supportation, dialkylaluminumcation enhanced MAO, surface bulky group modified MAO, and the like.MMAO may be produced by the hydrolysis of trimethylaluminum and a highertrialkylaluminum such as triisobutylaluminum. Mixtures of differentaluminoxanes may also be used as the activator(s).

There are a variety of methods for preparing aluminoxanes suitable foruse in the present invention, non-limiting examples of which aredescribed in U.S. Pat. No. 4,665,208; U.S. Pat. No. 4,952,540; U.S. Pat.No. 5,041,584; U.S. Pat. No. 5,091,352; U.S. Pat. No. 5,206,199; U.S.Pat. No. 5,204,419; U.S. Pat. No. 4,874,734; U.S. Pat. No. 4,924,018;U.S. Pat. No. 4,908,463; U.S. Pat. No. 4,968,827; U.S. Pat. No.5,308,815; U.S. Pat. No. 5,329,032; U.S. Pat. No. 5,248,801; U.S. Pat.No. 5,235,081; U.S. Pat. No. 5,157,137; U.S. Pat. No. 5,103,031; U.S.Pat. No. 5,391,793; U.S. Pat. No. 5,391,529; U.S. Pat. No. 5,693,838;U.S. Pat. No. 5,731,253; U.S. Pat. No. 5,731,451; U.S. Pat. No.5,744,656; U.S. Pat. No. 5,847,177; U.S. Pat. No. 5,854,166; U.S. Pat.No. 5,856,256; U.S. Pat. No. 5,939,346; EP 0 561 476; EP 0 279 586; EP 0594-218; EP 0 586 665; WO 94/10180; WO 99/15534; halogenated MAO aredescribed in U.S. Pat. No. 7,960,488; U.S. Pat. No. 7,355,058; and U.S.Pat. No. 8,354,485; dialkylaluminum cation enhanced MAO are described inUS 2013/0345376; and surface bulky group modified supported MAO aredescribed in U.S. Pat. No. 8,895,465; all of which are herein fullyincorporated by reference.

Optional Scavengers or Co-Activators:

In addition to the activator compounds, scavengers or co-activators maybe used. Suitable co-activators may be selected from the groupconsisting of: trialkylaluminum, dialkylmagnesium, alkylmagnesiumhalide, and dialkylzinc. Aluminum alkyl or organoaluminum compounds,which may be utilized as scavengers or co-activators, include, forexample, trimethylaluminum, triethylaluminum, triisobutylaluminum,tri-n-hexylaluminum, tri-n-octylaluminum, and the like. Other oxophilicspecies, such as diethyl zinc may be used. As mentioned above, theorganometallic compound used to treat the calcined support material maybe a scavenger or co-activator, or may be the same as or different fromthe scavenger or co-activator. In an embodiment, the co-activator isselected from the group consisting of: trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-octylaluminum,trihexylaluminum, and diethylzinc (alternately the group consisting of:trimethylaluminum, triethylaluminum, triisobutylaluminum,trihexylaluminum, tri-n-octylaluminum, dimethylmagnesium,diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, diisobutylmagnesium, dihexylmagnesium, dioctylmagnesium,methylmagnesium chloride, ethylmagnesium chloride, propylmagnesiumchloride, isopropylmagnesium chloride, butyl magnesium chloride,isobutylmagnesium chloride, hexylmagnesium chloride, octylmagnesiumchloride, methylmagnesium fluoride, ethylmagnesium fluoride,propylmagnesium fluoride, isopropylmagnesium fluoride, butyl magnesiumfluoride, isobutylmagnesium fluoride, hexylmagnesium fluoride,octylmagnesium fluoride, dimethylzinc, diethylzic, dipropylzinc, anddibutylzinc).

Metallocene Catalyst Precursor Compounds:

According to some embodiments of the invention, the single site catalystprecursor compound is represented by the following formula:(Cp)_(m)R^(A) _(n)M⁴Q_(k); wherein each Cp is a cyclopentadienyl or acyclopentadienyl substituted by one or more hydrocarbyl radicals havingfrom 1 to 20 carbon atoms; R^(A) is a structural bridge between two Cprings; M⁴ is a transition metal selected from groups 4 or 5; Q is ahydride or a hydrocarbyl group having from 1 to 20 carbon atoms or analkenyl group having from 2 to 20 carbon atoms, or a halogen; m is 1, 2,or 3, with the proviso that if m is 2 or 3, each Cp may be the same ordifferent; n is 0 or 1, with the proviso that n=0 if m=1; and k is suchthat k+m is equal to the oxidation state of M⁴, with the proviso that ifk is greater than 1, each Q may be the same or different.

According to some embodiments of the invention, the single site catalystprecursor compound is represented by the formula:R^(A)(CpR″_(p))(CpR*_(q))M⁵Q_(r); wherein each Cp is a cyclopentadienylor substituted cyclopentadienyl ring; each R* and R″ is a hydrocarbylgroup having from 1 to 20 carbon atoms and may be the same or different;p is 0, 1, 2, 3, or 4; q is 1, 2, 3, or 4; R^(A) is a structural bridgebetween the Cp rings imparting stereorigidity to the metallocenecompound; M⁵ is a group 4, 5, or 6 metal; Q is a hydrocarbyl radicalhaving from 1 to 20 carbon atoms or is a halogen; r is s minus 2, wheres is the valence of M⁵; wherein (CpR*_(q)) has bilateral orpseudobilateral symmetry; R*_(q) is selected, alkyl substituted indenyl,or tetra-, tri-, or dialkyl substituted cyclopentadienyl radical; and(CpR″_(p)) contains a bulky group in one and only one of the distalpositions; wherein the bulky group is of the formula AR^(W) _(V); andwhere A is chosen from group 4 metals, oxygen, or nitrogen, and R^(W) isa methyl radical or phenyl radical, and v is the valence of A minus 1.

According to some embodiments of the invention, the single site catalystprecursor compound is represented by the formula:

where M is a group 4, 5, or 6 metal; T is a bridging group; each X is,independently, an anionic leaving group; each R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is, independently, halogen atom,hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl,substituted germylcarbyl substituent or a —NR′₂, —SR′, —OR′, —OSiR′₃ or—PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group.

According to some embodiments of the invention, at least one of R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is a cyclopropylsubstituent represented by the formula:

wherein each R′ in the cyclopropyl substituent is, independently,hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbylgroup, or a halogen.

According to some embodiments of the invention, the M is selected fromtitanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum and tungsten;

each X is independently selected from hydrogen, halogen, hydroxy,substituted or unsubstituted C₁ to C₁₀ alkyl groups, substituted orunsubstituted C₁ to C₁₀ alkoxy groups, substituted or unsubstituted C₆to C₁₄ aryl groups, substituted or unsubstituted C₆ to C₁₄ aryloxygroups, substituted or unsubstituted C₂ to C₁₀ alkenyl groups,substituted or unsubstituted C₇ to C₄₀ arylalkyl groups, substituted orunsubstituted C₇ to C₄₀ alkylaryl groups and substituted orunsubstituted C₇ to C₄₀ arylalkenyl groups; or optionally, are joinedtogether to form a C₄ to C₄₀ alkanediyl group, or a conjugated C₄ to C₄₀diene ligand, which is coordinated to M in a metallacyclopentenefashion; or, optionally, represent a conjugated diene, optionally,substituted with one or more groups independently selected fromhydrocarbyl, trihydrocarbylsilyl, and trihydrocarbylsilylhydrocarbylgroups, said diene having a total of up to 40 atoms not countinghydrogen and forming a it complex with M; each R², R⁴, R⁸, and R¹⁰ isindependently selected from hydrogen, halogen, substituted orunsubstituted C₁ to C₁₀ alkyl groups, substituted or unsubstituted C₆ toC₁₄ aryl groups, substituted or unsubstituted C₂ to C₁₀ alkenyl groups,substituted or unsubstituted C₇ to C₄₀ arylalkyl groups, substituted orunsubstituted C₇ to C₄₀ alkylaryl groups, substituted or unsubstitutedC₈ to C₄₀ arylalkenyl groups, and —NR′₂, —SR′, —OR′, —SiR′₃, —OSiR′₃,and —PR′₂ radicals wherein each R′ is independently selected fromhalogen, substituted or unsubstituted C₁ to C₁₀ alkyl groups andsubstituted or unsubstituted C₆ to C₁₄ aryl groups; R³, R⁵, R⁶, R⁷, R⁹,R¹¹, R¹², and R¹³ are each selected from the group consisting ofhydrogen, halogen, hydroxy, substituted or unsubstituted C₁ to C₁₀ alkylgroups, substituted or unsubstituted C₁ to C₁₀ alkoxy groups,substituted or unsubstituted C₆ to C₁₄ aryl groups, substituted orunsubstituted C₆ to C₁₄ aryloxy groups, substituted or unsubstituted C₂to C₁₀ alkenyl groups, substituted or unsubstituted C₇ to C₄₀ arylalkylgroups, substituted or unsubstituted C₇ to C₄₀ alkylaryl groups, and C₇to C₄₀ substituted or unsubstituted arylalkenyl groups; and T isselected from:

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, and —P(O)(R¹⁴)—; wherein R¹⁴, R¹⁵, and R¹⁶ are eachindependently selected from hydrogen, halogen, C₁ to C₂₀ alkyl groups,C₆ to C₃₀ aryl groups, C₁ to C₂₀ alkoxy groups, C₂ to C₂₀ alkenylgroups, C₇ to C₄₀ arylalkyl groups, C₈ to C₄₀ arylalkenyl groups, and C₇to C₄₀ alkylaryl groups, optionally, R¹⁴ and R¹⁵, together with theatom(s) connecting them, form a ring; and M³ is selected from carbon,silicon, germanium, and tin; or T is represented by the formula:

wherein R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ are eachindependently selected from hydrogen, halogen, hydroxy, substituted orunsubstituted C₁ to C₁₀ alkyl groups, substituted or unsubstituted C₁ toC₁₀ alkoxy groups, substituted or unsubstituted C₆ to C₁₄ aryl groups,substituted or unsubstituted C₆ to C₁₄ aryloxy groups, substituted orunsubstituted C₂ to C₁₀ alkenyl groups, substituted or unsubstituted C₇to C₄₀ alkylaryl groups, substituted or unsubstituted C₇ to C₄₀alkylaryl groups, and substituted or unsubstituted C₈ to C₄₀ arylalkenylgroups; optionally two or more adjacent radicals R¹⁷, R¹⁸, R¹⁹, R²⁰,R²¹, R²², R²³, and R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them, form one or more rings; and M² represents one or morecarbon atoms, or a silicon, germanium, or tin atom.

In some embodiments, two or more different catalyst compounds arepresent in the catalyst systems used herein. In some embodiments, two ormore different catalyst systems are present in the reaction zone wherethe process(es) described herein occur. When two transition metalcompound based catalysts are used in one reactor as a mixed catalystsystem, the two transition metal compounds should be chosen such thatthe two are compatible. A simple screening method such as by ¹H or ¹³CNMR, known to those of ordinary skill in the art, can be used todetermine which transition metal compounds are compatible.

The two transition metal compounds (pre-catalysts) may be used in anyratio. Preferred molar ratios of (A) transition metal compound to (B)transition metal compound fall within the range of (A:B) 1:1000 to1000:1, alternatively 1:100 to 500:1, alternatively 1:10 to 200:1,alternatively 1:1 to 100:1, and alternatively 1:1 to 75:1, andalternatively 5:1 to 50:1. The particular ratio chosen will depend onthe exact pre-catalysts chosen, the method of activation, and the endproduct desired. Useful mole percentages, based upon the molecularweight of the pre-catalysts, are 10 to 99.9 mol % A to 0.1 to 90 mol %B, alternatively 25 to 99 mol % A to 0.5 to 50 mol % B, alternatively 50to 99 mol % A to 1 to 25 mol % B, and alternatively 75 to 99 mol % A to1 to 10 mol % B.

In any embodiment of the invention, in any embodiment of any formuladescribed herein, M may be Zr or Hf.

In any embodiment of the invention in any embodiment of any formuladescribed herein, each X is, independently, selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, alkoxides, sulfides, phosphides, halides, dienes,amines, phosphines, ethers, and a combination thereof, (two X's may forma part of a fused ring or a ring system), preferably each X isindependently selected from halides and C₁ to C₅ alkyl groups,preferably each X is a methyl group.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, each R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², or R¹³ is,independently, hydrogen or a substituted hydrocarbyl group orunsubstituted hydrocarbyl group, or a heteroatom, preferably hydrogen,methyl, ethyl, propyl, butyl, pentyl, hexyl, or an isomer thereof.

In a preferred embodiment of any formula described herein, each R³, R⁴,R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹¹, R¹², or R¹³ is, independently selected fromhydrogen, methyl, ethyl, phenyl, benzyl, cyclobutyl, cyclopentyl,cyclohexyl, naphthyl, anthracenyl, carbazolyl, indolyl, pyrrolyl,cyclopenta[b]thiopheneyl, fluoro, chloro, bromo, iodo, and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methylphenyl,dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl,dipropylphenyl, butylphenyl, dibutylphenyl, methylbenzyl,methylpyrrolyl, dimethylpyrrolyl, methylindolyl, dimethylindolyl,methylcarbazolyl, dimethylcarbazolyl, methylcyclopenta[b]thiopheneyldimethylcyclopenta[b]thiopheneyl.

In an embodiment of the invention in any embodiment of any formuladescribed herein, T is a bridging group and comprises Si, Ge, or C,preferably T is dialkyl silicon or dialkyl germanium, preferably T isdimethyl silicon.

In an embodiment of the invention in any embodiment of any formuladescribed herein, T is a bridging group and is represented by R′₂C,R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′,R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂,R′₂CSiR′₂, R′₂SiSiR′₂, R₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂,R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂,R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂,R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂,R′₂CR′₂C—S—R₂CR′₂, R′₂C—S—R′₂CR′₂, R′₂C—S—R′═CR′, R′₂C—Se—CR′₂,R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′,R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, or R′₂C—PR′—CR′₂, where each R′ is,independently, hydrogen or a C₁ to C₂₀ containing hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbylor germylcarbyl substituent, and, optionally, two or more adjacent R′may join to form a substituted or unsubstituted, saturated, partiallyunsaturated or aromatic, cyclic or polycyclic substituent. Preferably, Tis CH₂, CH₂CH₂, C(CH₃)₂, SiMe₂, SiPh₂, SiMePh, silylcyclobutyl(Si(CH₂)₃), (Ph)₂C, (p-(Et)₃SiPh)₂C, cyclopentasilylene (Si(CH₂)₄), orSi(CH₂)₅.

In embodiments of the invention, in any formula described herein, eachR² and R⁸, is independently, a C₁ to C₂₀ hydrocarbyl, or a C₁ to C₂₀substituted hydrocarbyl, C₁ to C₂₀ halocarbyl, C₁ to C₂₀ substitutedhalocarbyl, C₁ to C₂₀ silylcarbyl, C₁ to C₂₀ substituted silylcarbyl, C₁to C₂₀ germylcarbyl, or C₁ to C₂₀ substituted germylcarbyl substituents.Preferably, each R² and R⁸, is independently, methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl oran isomer thereof, preferably cyclopropyl, cyclohexyl, (1-cyclohexylmethyl) methyl, isopropyl, and the like.

In embodiments of the invention, in any embodiment of any formuladescribed herein, R⁴ and R¹⁰ are, independently, a substituted orunsubstituted aryl group. Preferred substituted aryl groups include arylgroups where a hydrogen has been replaced by a hydrocarbyl, or asubstituted hydrocarbyl, halocarbyl, substituted halocarbyl,silylcarbyl, substituted silylcarbyl, germylcarbyl, or substitutedgermylcarbyl substituents, a heteroatom or heteroatom-containing group.

In a preferred embodiment of the invention in any embodiment of anyformula described herein, R² and R⁸ are a C₁ to C₂₀ hydrocarbyl, such asmethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl or an isomer thereof, preferably cyclopropyl,cyclohexyl, (1-cyclohexyl methyl) methyl, or isopropyl; and R⁴ and R¹⁰are independently selected from phenyl, naphthyl, anthracenyl,2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl,3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl,2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl,4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl,2,6-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl,3-isopropylphenyl, 4-isopropylphenyl, 3,5-di-isopropylphenyl,2,5-di-isopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl,4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 2,5-di-tert-butylphenyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, carbazolyl, indolyl,pyrrolyl, or cyclopenta[b]thiopheneyl. In a preferred embodiment, R²,R⁸, R⁴ and R¹⁰ are as described in the preceding sentence and R³, R⁵,R⁶, R⁷, R⁹, R¹¹, R¹², and R¹³ are hydrogen.

In embodiments according to the present invention, suitable MCNcompounds are represented by the formula (1):A_(e)MX_(n-e);or the formula (Ic):TA₂MX_(n-2);wherein: e is 1 or 2; T is a bridging group between two A groups; each Ais a substituted monocyclic or polycyclic ligand that is pi-bonded to Mand, optionally, includes one or more ring heteroatoms selected fromboron, a group 14 atom that is not carbon, a group 15 atom, or a group16 atom, and when e is 2 each A may be the same or different, providedthat at least one A is substituted with at least one cyclopropylsubstituent directly bonded to any sp² carbon atom at a bondable ringposition of the ligand, wherein the cyclopropyl substituent isrepresented by the formula:

where each R′ is, independently, hydrogen, a substituted orunsubstituted hydrocarbyl group, or a halogen; M is a transition metalatom having a coordination number of n and selected from group 3, 4, or5 of the Periodic Table of Elements, or a lanthanide metal atom, oractinide metal atom; n is 3, 4, or 5; and each X is a univalent anionicligand, or two X's are joined and bound to the metal atom to form ametallocycle ring, or two X's are joined to form a chelating ligand, adiene ligand, or an alkylidene ligand.

In embodiments according to the present invention, the MCN compound maybe represented by the formula:T_(y)(A)_(e)(E)MX_(n-e-1)where E is J-R″_(x-1-y), J is a heteroatom with a coordination number ofthree from group 15 or with a coordination number of two from group 16of the Periodic Table of Elements; R″ is a C₁-C₁₀₀ substituted orunsubstituted hydrocarbyl radical; x is the coordination number of theheteroatom J where “x-1-y” indicates the number of R″ substituentsbonded to J; T is a bridging group between A and E, A and E are bound toM, y is 0 or 1; and A, e, M, X, and n are as defined above.

In embodiments according to the present invention, the MCN compound maybe represented by one of the following formulae:

where M, T, X, are as defined in claim 1; J, R″, and n are as definedabove, andeach R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, or R¹⁴ is,independently, hydrogen, a substituted hydrocarbyl group, anunsubstituted hydrocarbyl group, or a halide, provided that in formula1a and 1b, at least one of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, or R¹⁴ is a cyclopropyl substituent and in formula 2a and 2bat least one of R¹, R², R³, R⁴, R⁵, R⁶, or R⁷, is a cyclopropylsubstituent; and provided that any adjacent R¹ to R¹⁴ groups that arenot a cyclopropyl substituent, may form a fused ring or multicenterfused ring system where the rings may be aromatic, partially saturated,or saturated.

In embodiments according to the present invention, at least one A is amonocyclic ligand selected from the group consisting of substituted orunsubstituted cyclopentadienyl, heterocyclopentadienyl, and heterophenylligands provided that when e is one, the monocyclic ligand issubstituted with at least one cyclopropyl substituent, at least one A isa polycyclic ligand selected from the group consisting of substituted orunsubstituted indenyl, fluorenyl, cyclopenta[a]naphthyl,cyclopenta[b]naphthyl, heteropentalenyl, heterocyclopentapentalenyl,heteroindenyl, heterofluorenyl, heterocyclopentanaphthyl,heterocyclopentaindenyl, and heterobenzocyclopentaindenyl ligands.

MCN compounds suitable for use herein may further include one or moreof: dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)zirconiumdichloride; dimethylsilylene-bis(2-cyclopropyl-4-phenylindenyl)hafniumdichloride; dimethylsilylene-bis(2-methyl-4-phenylindenyl)zirconiumdichloride; dimethylsilylene-bis(2-methyl-4-phenylindenyl)hafniumdichloride; dimethylsilylene-bis(2-methyl-4-orthobiphenylindenyl)hafniumdichloride;dimethylsilylene-bis(2-methyl-4-orthobiphenylindenyl)zirconiumdichloride;dimethylsilylene-(2-cyclopropyl-4-orthobiphenylindenyl(2-methyl-4-3′,5′-di-t-butylphenylindenyl)hafniumdichloride;dimethylsilylene-(2-cyclopropyl-4-orthobiphenylindenylX2-methyl-4-3′,5′-di-t-butylphenylindenyl)zirconiumdichloride; dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenyl indenyl) zirconium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenyl indenyl) hafnium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl) (2-methyl,4-t-butylindenyl) zirconium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl) (2-methyl,4-t-butylindenyl) hafnium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindacenyl) zirconium dichloride;dimethylsilylene-(2-isopropyl-4(4-t-butyl)phenyl)indenyl)(2-methyl-4-phenylindacenyl) hafnium dichloride; dimethylsilylene(4-o-Biphenyl-2-(1-methylcyclohexyl)methyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl) zirconium dichloride; anddimethylsilylene (4-o-Biphenyl-2-(1-methylcyclohexyl)methyl-indenyl)(4-(3,5-di-tert-butylphenyl)-2-methyl-indenyl) hafnium dichloride;where, in alternate embodiments, the dichloride in any of the compoundslisted above may be replaced with dialkyl (such as dimethyl), dialkaryl,diflouride, diiodide, or dibromide, or a combination thereof.

Chain Transfer Agents:

This invention further relates to methods to polymerize olefins usingthe above complex in the presence of a chain transfer agent (“CTA”). TheCTA can be any desirable chemical compound such as those disclosed in WO2007/130306. Preferably, the CTA is selected from Group 2, 12, or 13alkyl or aryl compounds; preferably zinc, magnesium or aluminum alkylsor aryls; preferably where the alkyl is a C₁ to C₃₀ alkyl, alternately aC₂ to C₂₀ alkyl, alternately a C₃ to C₁₂ alkyl, typically selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, anddodecyl; e.g., dialkyl zinc compounds, where the alkyl is selectedindependently from methyl, ethyl, propyl, butyl, isobutyl, tertbutyl,pentyl, hexyl, cyclohexyl, and phenyl, where di-ethylzinc isparticularly preferred; or e.g., trialkyl aluminum compounds, where thealkyl is selected independently from methyl, ethyl, propyl, butyl,isobutyl, tertbutyl, pentyl, hexyl, cyclohexyl, and phenyl; or e.g.,diethyl aluminum chloride, diisobutylaluminum hydride, diethylaluminumhydride, di-n-octylaluminum hydride, dibutylmagnesium, diethylmagnesium,dihexylmagnesium, and triethylboron.

Useful CTAs are typically present at from 10 or 20 or 50 or 100equivalents to 600 or 700 or 800 or 1000 equivalents relative to thecatalyst component. Alternately, the CTA is preset at a catalystcomplex-to-CTA molar ratio of from about 1:3000 to 10:1; alternatively1:2000 to 10:1; alternatively 1:1000 to 10:1; alternatively, 1:500 to1:1; alternatively 1:300 to 1:1; alternatively 1:200 to 1:1;alternatively 1:100 to 1:1; alternatively 1:50 to 1:1; or/andalternatively 1:10 to 1:1.

Monomers:

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, preferably C₂ to C₂₀ alpha olefins, preferably C₂ to C₁₂alpha olefins, preferably ethylene, propylene, butene, pentene, hexene,heptene, octene, nonene, decene, undecene, dodecene, and isomersthereof. In a preferred embodiment, the monomer comprises propylene andoptional co-monomer(s) comprising one or more of ethylene or C₄ to C₄₀olefins, preferably C₄ to C₂₀ olefins, or preferably C₆ to C₁₂ olefins.The C₄ to C₄₀ olefin monomers may be linear, branched, or cyclic. The C₄to C₄₀ cyclic olefins may be strained or unstrained, monocyclic orpolycyclic, and may, optionally, include heteroatoms and/or one or morefunctional groups. In a preferred embodiment of the invention, themonomer is propylene and no comonomer is present.

Exemplary C₂ to C₄₀ olefin monomers and, optional, comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, preferably hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, preferablynorbornene, norbornadiene, and dicyclopentadiene.

One or more dienes may be present in the polymer produced herein at upto 10 wt %, preferably at 0.00001 to 1.0 wt %, preferably 0.002 to 0.5wt %, even more preferably 0.003 to 0.2 wt %, based upon the totalweight of the composition. In some embodiments 500 ppm or less of dieneis added to the polymerization, preferably 400 ppm or less, preferably300 ppm or less. In other embodiments, at least 50 ppm of diene is addedto the polymerization, or 100 ppm or more, or 150 ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, preferably C₄ to C₃₀, having at least two unsaturated bonds,wherein at least two of the unsaturated bonds are readily incorporatedinto a polymer by either a stereospecific or a non-stereospecificcatalyst(s). The diolefin monomers may be selected from alpha,omega-diene monomers (i.e., di-vinyl monomers). The diolefin monomersmay be linear di-vinyl monomers, most preferably those containing from 4to 30 carbon atoms. Examples of preferred dienes include butadiene,pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene,undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene, or higher ring containing diolefins with or withoutsubstituents at various ring positions.

The polymerization or copolymerization may be carried out using olefinssuch as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and1-octene, vinylcyclohexane, norbornene, and norbornadiene. Inparticular, propylene and ethylene are polymerized.

Preferably, the comonomer(s) are present in the final propylene polymercomposition at less than 50 mol %, preferably from 0.5 to 45 mol %,preferably from 1 to 30 mol %, preferably from 3 to 25 mol %, preferablyfrom 5 to 20 mol %, preferably from 7 to 15 mol %, with the balance ofthe copolymer being made up of the main monomer (e.g., propylene).

Polymerization:

The invention relates to polymerization processes where monomer and,optionally, comonomer are contacted with a catalyst system comprising anactivator and at least one metallocene compound, as described above. Thecatalyst compound and activator may be combined in any order, and arecombined typically prior to contacting with the monomer.

Polymerization processes of this invention can be carried out in anymanner known in the art. Any suspension, homogeneous, bulk, solution,slurry, or gas phase polymerization process known in the art can beused. Such processes can be run in a batch, semi-batch, or continuousmode. Homogeneous polymerization processes and slurry processes areuseful. (A homogeneous polymerization process is defined to be a processwhere at least 90 wt % of the product is soluble in the reaction media.)A bulk homogeneous process is also useful. (A bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 vol % or more.) Alternately, no solvent or diluent is present oradded in the reaction medium, (except for the small amounts used as thecarrier for the catalyst system or other additives, or amounts typicallyfound with the monomer; e.g., propane in propylene). In anotherembodiment, the process is a slurry process. As used herein the term“slurry polymerization process” means a polymerization process where asupported catalyst is employed and monomers are polymerized on thesupported catalyst particles. At least 95 wt % of polymer productsderived from the supported catalyst are in granular form as solidparticles (not dissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In a preferred embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In another embodiment, thesolvent is not aromatic, preferably aromatics are present in the solventat less than 1 wt %, preferably less than 0.5 wt %, preferably less than0 wt %, based upon the weight of the solvents.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Typical temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., preferably about 20° C. to about 200° C., preferablyabout 35° C. to about 150° C., preferably from about 40° C. to about120° C., preferably from about 45° C. to about 80° C.; and a pressure inthe range of from about 0.35 MPa to about 10 MPa, preferably from about0.45 MPa to about 6 MPa, or preferably from about 0.5 MPa to about 4MPa.

Propylene polymer compositions, according to embodiments of theinvention, may be prepared using conventional polymerization processessuch as a two-stage process in two reactors or a three-stage process inthree reactors, although it is also possible to produce thesecompositions in a single reactor. Each stage may be independentlycarried out in either the gas, solution, or liquid slurry phase. Forexample, the first stage may be conducted in the gas phase and thesecond in liquid slurry, or vice versa, and the, optional, third stagein gas or slurry phase. Alternatively, each phase may be the same in thevarious stages. Propylene polymer compositions of this invention can beproduced in multiple reactors, such as two or three, operated in series,where a component is polymerized first in a gas phase, liquid slurry orsolution polymerization process and another component is polymerized ina second reactor such as a gas phase or slurry phase reactor.

The stages of the processes of this invention can be carried out in anymanner known in the art, in solution, in suspension or in the gas phase,continuously or batch wise, or any combination thereof, in one or moresteps. The term “gas phase polymerization” refers to the state of themonomers during polymerization, where the “gas phase” refers to thevapor state of the monomers. In another embodiment, a slurry process isused in one or more stages. As used herein the term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles, and at least 95 wt % of polymer products derivedfrom the supported catalyst are in granular form as solid particles (notdissolved in the diluent). Gas phase polymerization processes can beused in one or more stages.

The productivity of the catalyst system in a single stage or in allstages combined may be at least 50, 500, 800, 5000, 10,000 or 20,000g(polymer)/g(cat)/hour.

Polymer Products:

The processes described herein can produce a variety of polymerproducts, including but not limited to ethylene and propylenehomopolymers and copolymers. The polymers produced may be homopolymersof ethylene or propylene or copolymers of ethylene preferably havingfrom 0 to 25 mol % (alternately from 0.5 to 20 mol %, alternately from 1to 15 mol %, preferably from 3 to 10 mol %) of one or more C₃ to C₂₀olefin comonomer (preferably C₃ to C₁₂ alpha-olefin, preferablypropylene, butene, hexene, octene, decene, dodecene, preferablypropylene, butene, hexene, octene), or are copolymers of propylenepreferably having from 0 to 25 mol % (alternately from 0.5 to 20 mol %,alternately from 1 to 15 mol %, preferably from 3 to 10 mol %) of one ormore of C₂ or C₄ to C₂₀ olefin comonomer (preferably ethylene or C₄ toC₁₂ alpha-olefin, preferably ethylene, butene, hexene, octene, decene,dodecene, preferably ethylene, butene, hexene, octene).

The polymers may comprise polypropylene, for example, iPP, highlyisotactic polypropylene, sPP, hPP, and RCP. The propylene polymer mayalso be heterophasic. The propylene polymer may also be an impactcopolymer (ICP). The ICP comprises a blend of iPP, preferably with aT_(m) of 120° C. or more, with a propylene polymer with a glasstransition temperature (T_(g)) of −30° C. or less and/or an ethylenepolymer.

The polymer produced herein may be combined with one or more additionalpolymers prior to being formed into a film, molded part, or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

EXPERIMENTAL

Silica was obtained from the Asahi Glass Co., Ltd. or AGC ChemicalsAmericas, Inc. (D100-100A, D150-60A), PQ Corporation (PD 14024, MS3065), Fuji Silysia Chemical Ltd. (P-3), and Davison Chemical Divisionof W.R. Grace and Company (G 948). MAO was obtained as a 30 wt % MAO intoluene solution from Albemarle (13.5 wt % Al or 5.0 mmol/g).

Calcination of Raw Silica:

Raw silica was calcined in a CARBOLITE Model VST 12/600 tube furnaceusing a EUROTHERM 3216P1 temperature controller, according to thefollowing procedure. The controller was programmed with the desiredtemperature profile. A quartz tube was filled with 100 g silica, and avalve was opened and adjusted to flow the nitrogen through the tube sothat the silica was completely fluidized. The quartz tube was thenplaced inside the heating zone of the furnace. The silica was heatedslowly to the desired temperature and held at this temperature for atleast 8 hours to allow complete calcination and removal of water ormoisture. After the dehydration was complete, the quartz tube was cooledto ambient temperature. Calcined silica was recovered in a silicacatcher, and collected into a glass container inside a dry box. Diffusereflectance infrared Fourier transform spectroscopy (DRIFTS) was used asa quality control check. The different silicas used in some of thefollowing examples and their calcination conditions are listed in Table1.

Supported MAO (sMAO) was prepared at reaction initiation temperatures of−20° C. to RT to reduce the risk of fragmentation of high SA, small PDsilica upon reaction with MAO; or at temperatures up to 100° C. or more,to facilitate higher MAO loading and/or stronger fixation to minimizeMAO leaching from the support. The sMAO preparation conditions arelisted in Table 2.

sMAO Method A (CsMAO1, sMAO 1-4a, sMAO 5-7):

For high temperature sMAO preparation, the following or a similarprocedure was used. X g of silica was slurried in a reactor with 10×gtoluene (see Table 2 for X). All slurry and solvent liquid ratios aregiven as weight ratios relative to the starting silica material, e.g.,raw silica or silica supported MAO and/or catalyst. The reactor wasstirred at 500 rpm. Cold (−20° C.) 30 wt % MAO at an amount of X*Y mmolAl based on Y mmol Al/g silica (see Table 2 for Y) was added slowly tomaintain the temperature of the reactor at or below 40° C. The reactorwas stirred for 30 minutes at 350 rpm at RT and then heated at 100° C.for 3 hours. The slurry was cooled to ambient temperature and filteredthrough a fine frit. The wet solid was washed with 10×g toluene and then10×g hexane twice, and then dried under vacuum for 3 hours, yielding Z gdry sMAO (see Table 2 for Z).

sMAO Method B (sMAO4b):

For low temperature sMAO preparation to minimize sMAO fragmentation, thefollowing or a similar procedure was used. X g silica was slurried in areactor with 10×g toluene (see Table 2 for X). The reactor was chilledin a freezer to −20° C. or maintained at RT. The reactor was stirred at500 rpm. Cold (−20° C.) 30 wt % MAO was added slowly to the reactor tomaintain the temperature below 40° C., and then the reactor was stirredat 350 rpm at RT for 3 hours. The mixture was filtered through a mediumfrit, and the wet solid washed with 10× toluene and then 10× hexane, anddried under a vacuum for 3 hours, yielding Z g dry sMAO (see Table 2 forZ).

TABLE 1 Silica Properties and Calcination Temperatures Tc PS SA PV PDSupport SiO₂ (° C.) (um) (m²/g) (mL/g) (nm (Å)) CS1 G 948 600 58 2781.68 24.2 (242) S1 PD 14024 200 85 611 1.40 9.2 (92) S2 D100-100A 200100 543 1.51 11.1 (111) S3 P-3 200 33 690 1.13 6.6 (66) S4a D150-60A 200150 733 1.17 6.4 (64) S4b D150-60A 600 150 733 1.17 6.4 (64) S5 MS 3065200 90 650 3.0 18.5 (185) S6 PD 13054 200 130 671 1.11 6.6 (66) S7D70-120A 600 70 450 1.64 14.6 (146) Tc—Calcination temperature;PS—average particle size (from manufacturer); SA—BET surface area (frommanufacturer); PV—pore volume (from manufacturer); PD—pore diameter(from manufacturer)

TABLE 2 Supported MAO Preparation MAO X Silica MAO^(a) T1^(b) Time^(c) ZYield MAO Loading^(d) Loading^(e) sMAO # Silica # (g) (Y mmol Al/g) (°C.) (hr) (g) (mmol Al/g silica) (wt %) CsMAO1 CS1 5.0 9.5 100 3 7.077.02 29.3 sMAO1 S1 10.05 13 100 3 17.85 13.2 41.2 sMAO2 S2 1.00 13 100 31.70 11.9 41.2 sMAO3 S3 1.04 13 100 3 1.81 12.5 42.5 sMAO4a S4a 5.0811.5 100 3 8.61 11.8^(f) 41.0 xMAO4b S4b 5.0 7.0 −20 3 7.00 6.8 28.6sMAO5 S5 5.12 15 100 3 9.54 14.6 46.3 sMAO6 S6 5.04 11 100 3 8.4211.4^(f) 40.1 sMAO7 S7 10.0 12 100 3 18.06 13.7 44.6 ^(a)MAO charge intotal mmol Al/g silica; ^(b)Reaction temperature T1 after MAO addition;^(c)Reaction time at T1; ^(d)MAO loading as mmol Al/g silica, calculatedas ((Z − X)/59)/X, where 59 is the estimated Mw of MAO on silica;^(e)MAO loading as wt % of total sMAO weight, calculated as (Z − X)/Z;^(f)MAO solid leaching occurred.

Example CsMAO1 in Table 2 shows that the conventional silica, G 948, hasan MAO loading that is substantially less than almost all of the otherexamples in the table.

Example sMAO1 uses PD 14024. FIG. 1 is an electron micrograph of PD14024, a high surface area silica with a pore volume that is justslightly lower than the conventional silica G 948. The pore diameter,therefore, is much smaller than that of G 948, but still sufficient forthe MAO molecules to enter the pores leading to a high MAO loading. FIG.2 is an electron micrograph of the MAO supported on PD 14024 silica,with an aluminoxane loading of 13.2 mmol Al/g silica. The aluminoxaneloading is high and particle fragmentation and MAO leaching are notobserved. FIG. 3 is a plot of the pore diameter distribution for raw PD14024 silica versus the pore diameter distributions for MAO supported onPD 14024 silica at aluminoxane loadings of about 9, 11, and 13 mmol Al/gsilica. FIG. 3 shows that a significant portion of the incremental porevolume in the raw PD 14024 silica is comprised of pores having a porediameter larger than about 100 Angstrom. This will be discussed furtherbelow.

Example sMAO2 uses D 100-100A silica with a slightly lower surface areathan PD 14024 but similar pore volume and thus slightly larger porediameter. The MAO loading is slightly lower than PD 14024 in sMAO1likely due to the smaller surface area, but still improved over the G948 conventional silica. Particle fragmentation and MAO leaching werenot observed.

Example sMAO3 uses P-3 silica with a very high surface area. FIG. 4 isan electron micrograph showing raw P-3 silica particles. The pore volumehas to be reduced to maintain mechanical strength, resulting in a porediameter of only about 66 Angstrom. FIG. 5 is an electron micrograph ofthe MAO supported on Fuji P-3 silica, with an aluminoxane loading of12.5 mmol Al/g silica. Although the aluminoxane loading for this silicais quite high, FIG. 5 when compared with FIG. 4 shows that sMAO particlefragmentation has occurred. This fragmentation is likely related to MAObecause the silica without MAO can be calcined at 600° C. and nofragmentation is observed.

Example sMAO4a uses D150-60A silica with an even higher surface areathan the P-3 silica of sMAO3. FIG. 6 is an electron micrograph showingraw D150-60A silica particles. FIG. 7 is an electron micrograph of theMAO supported on D150-60A silica, with an aluminoxane loading of 11.8mmol Al/g silica. Although the MAO loading for this silica is high, FIG.7 shows that particle fragmentation and MAO solid leaching haveoccurred. This fragmentation is again likely related to MAO because thesilica without MAO can be calcined at 600° C. and no fragmentation isobserved.

For comparison with sMAO4a, Example sMAO4b uses the same silica. InsMAO4b the fragmentation and leaching are controlled by reducing thereaction temperature to a value from −20° C. to RT. FIG. 8 is anelectron micrograph of MAO supported on D150-60A silica prepared atlower temperature, showing that particle fragmentation is minimal andMAO leaching is not observed. However, the aluminoxane loading inExample sMAO4b is much smaller. It is possible that the very largeparticle size of the silica in sMAO4b may be the reason why at reactiontemperatures of from −20° C. to RT the particles do not fragment. Thepore diameter is so small and the pores are so deep that MAO moleculesmay only reach partially to the end of the pores and block furtheraluminoxane loading. A higher reaction temperature may causefragmentation and open the pore structure to enable higher aluminoxaneloading.

Example sMAO5 uses MS 3065 silica. FIG. 9 is an electron micrograph ofthe raw MS 3065 silica after a simple scratch with a lab spatula. Thescratch causes significant particle fragmentation due to the highsurface area and high pore volume of the silica. The aluminoxane loadingin the MAO supported on MS 3065 is high, however.

As discussed above, although fragmented silica supported aluminoxanesmay not be suitable for some types of catalyst preparation orpolymerization reactor systems, they may be suitable for other types.For example, they may be suitable in catalyst preparation environmentswhere high agitation power is not involved, or in polymerization reactorsystems where catalyst particle size does not play a significant role orwhere MAO leaching is not as likely to be problematic (e.g., gas phasepolymerization reactor systems).

Example sMAO6 uses PD 13054 silica. FIG. 10 is an electron micrograph ofMAO supported on PD 13054 silica, with an aluminoxane loading of 11.4mmol Al/g silica. FIG. 10 shows that MAO solid leaching has occurred.

Example sMAO7 uses D70-120A silica. The MAO supported on D70-120A silicahad an aluminoxane loading of about 13.7 mmol Al/g silica, and particlefragmentation and leaching were not observed.

Example sMAO8 uses DM-M302 silica. The MAO supported on DM-M302 silicahas a very high aluminoxane loading of about 19.7 mmol Al/g silica.

Catalyst Preparation:

The following general procedure or a similar procedure was used. sMAOwas slurried in 4M g toluene (see Table 3). About 0.274 mmol neat TIBA/gsMAO was added slowly to the slurry with vigorous agitation for 10 min.Metallocene precursor at an amount of about N mg based on 0.0175 (mmolZr/g sMAO) was then mixed with the TIBA-treated sMAO slurry and themixture was agitated for 1-2 hours at RT (see Table 3). The slurry wasthen filtered, washed once with 5M g toluene and twice with 5M g hexane,and dried under vacuum for 2 hours, yielding O g (see Table 3). Thecatalyst precursor compounds used are provided in Table 4.

Polymerization Procedure:

The following general procedure or a similar procedure was used. A 2 Lautoclave reactor was used. A catalyst tube was loaded with 2 mL of a0.091 M tri-n-octylaluminum (TNOAL) solution in hexane and the solutionwas injected into the reactor in a nitrogen carrier. The catalyst tubewas then pressurized with 152 kPa (22 psi) of hydrogen gas (2.1 mmol)which was then injected into the reactor. Next, 600 mL of propylene in anitrogen carrier was added and the reactor was heated to 70° C. with astir rate of 500 rpm. A mineral oil slurry containing about 45 mg ofsolid catalyst was then loaded into a second catalyst tube as a drypowder, and inserted into the reactor along with 200 mL of propylene.Other conditions are listed under Table 2 for each run.

TABLE 3 Catalyst Preparation and Polymerization Results M sMAO N MCN OYield Activity sMAO# Cat. (g) (mg) (g) (g/g cat/hr) CsMAO1 CAT2 1.0 30 12,710 sMAO1 CAT1 1.0 17 0.98 7,600 sMAO2 CAT2 8.24 64 8.30 8,813 sMAO4aCAT2 1.0 14 1.0 10,553 sMAO4b CAT2 1.0 14 1.0 1,596 sMAO6 CAT2 3.1 613.55 10,042

TABLE 4 Catalysts Catalyst Catalyst precursor compound CAT1rac-dimethylsilyl (4-o-biphenyl-2-n-hexyl-indenyl) (2-methyl-4-(3′,5′-di-tert-butyl-4′-methoxy-phenyl)-indenyl) zirconiumdichloride CAT2 rac-dimethylsilyl bis(2-cyclopropyl-4-(3′,5′-di-tert-butylphenyl)-indenyl) zirconium dichloride

Pore Diameter and Pore Distribution:

The experiments below were completed using a MICROMERITICS ASAP 2420Surface Area and Porosity Analyzer. An intent of these experiments wasto identify the pore distribution most useful for increasing MAO loadingwhile limiting solid MAO leaching, with or without heating. A 2 g sampleof raw silica was loaded in the sample tube and degassed at 120° C. for4 hours, or a 2 g sample of sMAO was loaded in the sample tube anddegassed at 40° C. overnight, both under vacuum. A general experimentalprotocol designed by MICROMERITICS was used to determine the porevolumes and pore diameters for each diameter range, and the results areshown in Table 5 below for the raw D150-60A silica.

TABLE 5 Raw Silica Porosity Data for D150-60A PD Range (Å) Average PD(Å) Incremental PV (mL/g) 3384.5-1810.7 2155.8 0.00064 1810.7-955.4 1136.9 0.00094 955.4-723.4 806.8 0.00066 723.4-502.4 572.7 0.00126502.4-295.6 346.2 0.00333 295.6-202.3 230.9 0.00533 202.3-165.6 180.00.00929 165.6-140.3 150.7 0.02521 140.3-123.9 131.0 0.04604 123.9-114.3118.7 0.05800 114.3-110.6 112.4 0.02260 110.6-104.5 107.4 0.05447104.5-99.4  101.8 0.04118 99.4-93.6 96.3 0.05663 93.6-87.9 90.6 0.0639587.9-83.3 85.5 0.06405 83.3-79.0 81.1 0.04857 79.0-73.9 76.3 0.0607873.9-69.4 71.5 0.06230 69.4-64.9 67.0 0.05193 64.9-59.8 62.1 0.0639959.8-56.9 58.3 0.03246 56.9-51.9 54.1 0.05888 51.9-50.6 51.2 0.0141850.6-45.8 47.9 0.05167 45.8-44.8 45.3 0.01053 44.8-40.0 42.1 0.0477140.0-35.7 37.6 0.03921 35.7-32.0 33.6 0.03132 32.0-28.7 30.1 0.0252528.7-25.6 26.9 0.02154 25.6-23.1 24.2 0.01703 23.1-20.4 21.5 0.0169220.4-19.4 19.9 0.00613 19.4-18.4 18.9 0.00638 18.4-17.4 17.9 0.00657

Similar measurements were taken for raw silicas PD 14024, D100-100A, andD70-120A. For each silica, the sum of the incremental pore volumes withpore diameters larger than about 100 Angstrom are divided by the totalpore volumes to obtain the percentage of the incremental pore volumehaving pore diameters larger than about 100 Angstrom. Results aresummarized in Table 6.

TABLE 6 Pore Volume Summary Silica D150-60A D100-100A PD 14024 D70-120APV >100 Å PD (mL/g) 0.27 1.13 0.64 1.50 Total PV (mL/g) 1.13 1.53 1.361.70 Percent (%) >100 Å 23 74 47 89

All documents described herein are incorporated by reference herein forpurposes of all jurisdictions where such practice is allowed, includingany priority documents, related application and/or testing procedures tothe extent they are not inconsistent with this text. As is apparent fromthe foregoing general description and the specific embodiments, whileforms of the invention have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the invention belimited thereby. Likewise, the term “comprising” is consideredsynonymous with the term “including.” Likewise whenever a composition,an element or a group of elements is preceded with the transitionalphrase “comprising,” it is understood that we also contemplate the samecomposition or group of elements with transitional phrases “consistingessentially of,” “consisting of,” “selected from the group of consistingof,” or “is” preceding the recitation of the composition, element, orelements and vice versa.

What is claimed is:
 1. An olefin polymerization catalyst systemcomprising a silica support and a catalyst precursor compound, whereinthe silica support comprises: agglomerates of silica gel particleshaving: a. an average surface area of from about 400 to 800 m²/g; b. anaverage pore diameter of from about 60 to 180 Angstrom; c. at least 20%of the incremental pore volume comprised of pores having a pore diameterlarger than about 100 Angstrom and smaller than 1000 Angstrom; d. lessthan 20% of the incremental pore volume comprised of pores having a porediameter of 1000 Angstrom or more; e. a particle size of 30 to 200micrometers; and f. an average pore volume of from about 0.5 to 2.5 ml/gof silica; wherein the catalyst system further comprises an aluminoxane,and the aluminoxane loading on the support is 9.5 to 20 mmol Al/gsilica.
 2. The catalyst system of claim 1, wherein said silica gelparticles have an average surface area of from about 550 to 650 m²/g. 3.The catalyst system of claim 1, wherein said silica gel particles havean average pore diameter of from about 80 to 130 Angstrom.
 4. Thecatalyst system of claim 1, wherein said silica gel particles have anaverage pore volume of from about 1.0 to 2.0 ml/g of silica.
 5. Thecatalyst system of claim 1, wherein said silica gel particles have anaverage particle size of from about 50 to 200 micrometers.
 6. Thecatalyst system of claim 1, wherein at least 50% of the incremental porevolume is comprised of pores having a pore diameter larger than about100 Angstrom.
 7. The catalyst system of claim 1, wherein saidaluminoxane is methylaluminoxane.
 8. The catalyst system of claim 1,wherein the catalyst precursor compound is a single site catalystcomponent.
 9. The catalyst system of claim 1, wherein the catalystprecursor compound is a metallocene catalyst component.
 10. The catalystsystem of claim 1, wherein a raw silica surface area and a supportedaluminoxane surface area differ by about or less than 10%.
 11. Thecatalyst system of claim 1, wherein a raw silica particle size and asupported aluminoxane particle size differ by about or less than 10% ona volumetric basis.
 12. An olefin polymerization catalyst systemcomprising a silica support and a catalyst precursor compound, whereinthe silica support comprises silica gel particles having: a. an averagesurface area of from about 400 to 800 m²/g; b. an average pore diameterof from about 60 to 180 Angstrom; c. at least 20% of the incrementalpore volume comprised of pores having a pore diameter larger than about100 Angstrom and smaller than 1000 Angstrom; d. less than 20% of theincremental pore volume comprised of pores having a pore diameter of1000 Angstrom or more; e. a particle size of 30 to 200 micrometers; andf. an average pore volume of from about 0.5 to 2.5 ml/g of silica;wherein the catalyst system further comprises an aluminoxane, and thealuminoxane loading on the support is 9.5 to 20 mmol Al/g silica, andthe silica particles do not comprise agglomerates.
 13. A method formaking an olefin polymerization catalyst system comprising contacting: asilica support, wherein the silica support comprises silica gelparticles having: an average surface area of from about 400 to 800 m²/g;an average pore diameter of from about 60 to 180 Angstrom; a particlesize of 30 to 200 micrometers; and an average pore volume of from about0.5 to 2.5 ml/g of silica; and wherein at least 20% of the incrementalpore volume is comprised of pores having a pore diameter larger thanabout 100 Angstrom and smaller than 1000 Angstrom; and less than 20% ofthe incremental pore volume comprised of pores having a pore diameter of1000 Angstrom or more; an aluminoxane; and an olefin catalyst component,wherein the catalyst system has an aluminoxane loading on the support of9.5 to 20 mmol Al/g silica, and the support comprises agglomerates ofprimary particles having a size range of 50 nm to 50 μm.
 14. The methodof claim 13, wherein said silica gel particles have an average surfacearea of from about 500 to 700 m²/g.
 15. The method of claim 13, whereinsaid silica gel particles have an average pore volume of from about 0.1to 2.0 ml/g of silica.
 16. The method of claim 13, wherein said silicagel particles have an average particle size of from about 50 to 200micrometers.
 17. The method of claim 13, wherein at least 50% of theincremental pore volume is comprised of pores having a pore diameterlarger than about 100 Angstrom.
 18. The method of claim 13, wherein saidaluminoxane is methylaluminoxane.
 19. The method of claim 13, whereinsaid olefin catalyst component is a single site catalyst component. 20.The method of claim 13, wherein said olefin catalyst component is ametallocene catalyst component.
 21. The method of claim 13, wherein araw silica surface area and a supported aluminoxane surface area differby about or less than 10%, and/or wherein a raw silica particle size anda supported aluminoxane particle size differ by about or less than 10%on a volumetric basis.
 22. A method for making an olefin polymerizationcatalyst system comprising contacting: a silica support, wherein thesilica support comprises silica gel particles having: an average surfacearea of from about 400 to 800 m²/g; an average pore diameter of fromabout 60 to 180 Angstrom; a particle size of 30 to 200 micrometers; andan average pore volume of from about 0.5 to 2.5 ml/g of silica; whereinat least 20% of the incremental pore volume is comprised of pores havinga pore diameter larger than about 100 Angstrom and smaller than 1000Angstrom; and less than 20% of the incremental pore volume comprised ofpores having a pore diameter of 1000 Angstrom or more; an aluminoxane;and an olefin catalyst component, wherein the catalyst system has analuminoxane loading on the support of 9.5 to 20 mmol Al/g silica and thesilica particles do not comprise agglomerates.
 23. A method forpolymerizing olefins using the catalyst system of claim
 1. 24. Themethod of claim 13, wherein said aluminoxane loading is greater thanabout 12 to 20 mmol Al/g silica.
 25. The method of claim 1, wherein saidaluminoxane loading is greater than about 12 to 20 mmol Al/g silica. 26.The method of claim 1, wherein at least 50% of the incremental porevolume is comprised of pores having a pore diameter larger than about125 Angstrom and smaller than 900 Angstrom; and less than 20% of theincremental pore volume comprised of pores having a pore diameter of 900Angstrom or more.
 27. The method of claim 1, wherein at least 50% of theincremental pore volume is comprised of pores having a pore diameterlarger than about 150 Angstrom and smaller than 800 Angstrom; and lessthan 20% of the incremental pore volume comprised of pores having a porediameter of 800 Angstrom or more.
 28. The method of claim 13, wherein atleast 50% of the incremental pore volume is comprised of pores having apore diameter larger than about 125 Angstrom and smaller than 900Angstrom; and less than 20% of the incremental pore volume comprised ofpores having a pore diameter of 900 Angstrom or more.
 29. The method ofclaim 13, wherein at least 50% of the incremental pore volume iscomprised of pores having a pore diameter larger than about 150 Angstromand smaller than 800 Angstrom; and less than 20% of the incremental porevolume comprised of pores having a pore diameter of 800 Angstrom ormore.
 30. The olefin polymerization catalyst system of claim 1 whereinthe silica support comprises silica gel particles has an average porediameter of from about 90 to 180 Angstrom.
 31. The olefin polymerizationcatalyst system of claim 1 wherein the silica support comprises silicagel particles has an average pore diameter of from about 100 to 150Angstrom.
 32. The catalyst system of claim 1, wherein at least 50% ofthe incremental pore volume is comprised of pores having a pore diameterlarger than about 125 Angstrom and less than 20% of the incremental porevolume is comprised of pores having a pore diameter in the range ofabout 1000 Angstrom or more.
 33. The catalyst system of claim 1, whereinat least 70% of the incremental pore volume is comprised of pores havinga pore diameter larger than about 125 Angstrom and less than 20% of theincremental pore volume is comprised of pores having a pore diameter inthe range of about 800 Angstrom or more.
 34. The catalyst system ofclaim 1, wherein the difference between the raw silica particle size andthe supported aluminoxane particle size is less than 50%, on avolumetric basis.
 35. The catalyst system of claim 1, wherein thedifference between the raw silica particle size and the supportedaluminoxane particle size is less than 20%, on a volumetric basis.
 36. Amethod for polymerizing olefins comprising contacting olefins with thecatalyst system of claim 1 in a gas phase polymerization.
 37. Thecatalyst system of claim 1, wherein the catalyst precursor compound isrepresented by the formula:

where M is a group 4, 5, or 6 metal; T is a bridging group; each X is,independently, an anionic leaving group; each R², R³, R⁴, R⁵, R⁶, R⁷,R⁸, R⁹, R¹⁰, R¹¹, R¹², and R¹³ is, independently, halogen atom,hydrogen, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl,substituted germylcarbyl substituent or a —NR′₂, —SR′, —OR′, —OSiR′₃ or—PR′₂ radical, wherein R′ is one of a halogen atom, a C₁-C₁₀ alkylgroup, or a C₆-C₁₀ aryl group.
 38. The catalyst system of claim 37,wherein at least one of R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹²,and R¹³ is a cyclopropyl substituent represented by the formula:

wherein each R′ in the cyclopropyl substituent is, independently,hydrogen, a substituted hydrocarbyl group, an unsubstituted hydrocarbylgroup, or a halogen.
 39. The catalyst system of claim 37, wherein M isselected from titanium, zirconium, hafnium; each X is independentlyselected from hydrogen, halogen, hydroxy, substituted or unsubstitutedC₁ to C₁₀ alkyl groups, substituted or unsubstituted C₁ to C₁₀ alkoxygroups, substituted or unsubstituted C₆ to C₁₄ aryl groups, substitutedor unsubstituted C₆ to C₁₄ aryloxy groups, substituted or unsubstitutedC₂ to C₁₀ alkenyl groups, substituted or unsubstituted C₇ to C₄₀arylalkyl groups, substituted or unsubstituted C₇ to C₄₀ alkylarylgroups and substituted or unsubstituted C₇ to C₄₀ arylalkenyl groups; oroptionally, are joined together to form a C₄ to C₄₀ alkanediyl group, ora conjugated C₄ to C₄₀ diene ligand, or, optionally, represent aconjugated diene, optionally, substituted with one or more groupsindependently selected from hydrocarbyl, trihydrocarbylsilyl, andtrihydrocarbylsilylhydrocarbyl groups, said diene having a total of upto 40 atoms not counting hydrogen and forming a π complex with M; eachR², R⁴, R⁸, and R¹⁰ is independently selected from hydrogen, halogen,substituted or unsubstituted C₁ to C₁₀ alkyl groups, substituted orunsubstituted C₆ to C₁₄ aryl groups, substituted or unsubstituted C₂ toC₁₀ alkenyl groups, substituted or unsubstituted C₇ to C₄₀ arylalkylgroups, substituted or unsubstituted C₇ to C₄₀ alkylaryl groups,substituted or unsubstituted C₈ to C₄₀ arylalkenyl groups, and —NR′₂,—SR′, —OR′, —SiR′₃, —OSiR′₃, and —PR′₂ radicals wherein each R′ isindependently selected from halogen, substituted or unsubstituted C₁ toC₁₀ alkyl groups and substituted or unsubstituted C₆ to C₁₄ aryl groups;R³, R⁵, R⁶, R⁷, R⁹, R¹¹, R¹², and R¹³ are each selected from the groupconsisting of hydrogen, halogen, hydroxy, substituted or unsubstitutedC₁ to C₁₀ alkyl groups, substituted or unsubstituted C₁ to C₁₀ alkoxygroups, substituted or unsubstituted C₆ to C₁₄ aryl groups, substitutedor unsubstituted C₆ to C₁₄ aryloxy groups, substituted or unsubstitutedC₂ to C₁₀ alkenyl groups, substituted or unsubstituted C₇ to C₄₀arylalkyl groups, substituted or unsubstituted C₇ to C₄₀ alkylarylgroups, and C₇ to C₄₀ substituted or unsubstituted arylalkenyl groups;and T is selected from:

—B(R¹⁴)—, —Al(R¹⁴)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO₂—, —N(R¹⁴)—, —CO—,—P(R¹⁴)—, and —P(O)(R¹⁴)—; wherein R¹⁴, R¹⁵, and R¹⁶ are eachindependently selected from hydrogen, halogen, C₁ to C₂₀ alkyl groups,C₆ to C₃₀ aryl groups, C₁ to C₂₀ alkoxy groups, C₂ to C₂₀ alkenylgroups, C₇ to C₄₀ arylalkyl groups, C₈ to C₄₀ arylalkenyl groups, and C₇to C₄₀ alkylaryl groups, optionally, R¹⁴ and R¹⁵, together with theatom(s) connecting them, form a ring; and M³ is selected from carbon,silicon, germanium, or tin; or T is represented by the formula:

wherein R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, and R²⁴ are eachindependently selected from hydrogen, halogen, hydroxy, substituted orunsubstituted C₁ to C₁₀ alkyl groups, substituted or unsubstituted C₁ toC₁₀ alkoxy groups, substituted or unsubstituted C₆ to C₁₄ aryl groups,substituted or unsubstituted C₆ to C₁₄ aryloxy groups, substituted orunsubstituted C₂ to C₁₀ alkenyl groups, substituted or unsubstituted C₇to C₄₀ alkylaryl groups, substituted or unsubstituted C₇ to C₄₀alkylaryl groups, and substituted or unsubstituted C₈ to C₄₀ arylalkenylgroups; optionally two or more adjacent radicals R¹⁷, R¹⁸, R¹⁹, R²⁰,R²¹, R²², R²³, and R²⁴, including R²⁰ and R²¹, together with the atomsconnecting them, form one or more rings; and M² represents one or morecarbon atoms, or a silicon, germanium, or tin atom.
 40. The method ofclaim 1, wherein at least 85% of the incremental pore volume iscomprised of pores having a pore diameter larger than about 150 Angstromand smaller than 800 Angstrom; and less than 20% of the incremental porevolume comprised of pores having a pore diameter of 800 Angstrom ormore.